JPS61212556A - Substituted propalgyloxyacetthioamide derivative, production thereof, herbicide and agricultural and horticultural fungicide containing same - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (A is phenyl, substituted phenyl or naphthyl; R<1> is H, or lower alkyl; R<2> is H, alkyl, or haloalkyl). EXAMPLE:alpha-Benzoylamino-propalgyloxyacetthioamide. USE:A herbicide and an agricultural and horticultural fungicide showing weeding effects especially on weeds in paddy fields, and improved controlling action on phytophthora rot, black shank, late blight, downy mildew, dampling-off, etc., of various crops with a small amount of the agents in a low concentration. The agents can be obtained in a short process easily in high yield. PREPARATION:An acylaminoacetonitrile derivative shown by the formula II is reacted with gaseous hydrogen sulfide in the presence of a tertiary amine catalyst (e.g., triethylamine) in a proper solvent at -20-100 deg.C, preferably 20-50 deg.C, to give a compound shown by the formula I.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to the general formula (1) (wherein A represents a phenyl group, a substituted phenyl group or a naphthyl group, and R1 represents a hydrogen atom or a lower alkyl group, The present invention relates to a substituted propargyloxyacetothioamide derivative represented by (R1'' represents a hydrogen atom, an alkyl group, or a haloalkyl group), a method for producing the same, and a herbicide for paddy fields or a fungicide for agriculture and horticulture containing the same as an active ingredient.

[Prior art]

A great deal of research has been carried out on amide derivatives useful in agriculture and horticulture, and many compounds exhibiting characteristic physiological activities have been discovered and put into practical use.

For example, substituted p/zamide derivatives include ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (benzoylprop-ethyl) as a herbicide, and 2-methyl-N-benzoyl-N- as a fungicide. (3-impropoxyphenyl)benzamide (mepronil) and the like are known.

In addition, as an acetothioamide derivative, JP-A-57-15
Herbicides and fungicides are disclosed in Japanese Patent No. 7978 and No. 57-176938. Among them, JP-A-57-176
No. 958 discloses ethoxyacetothioamide derivatives, but there is no description of substituted propargyloxyacetothioamide derivatives. Furthermore, JP-A-57-176938 mentions the use of alkoxyacetothioamide derivatives as fungicides and herbicides.

Herbicides have been tested for their herbicidal activity before and after germination, as well as their phytotoxicity against sugar beets, rapeseed, cotton, soybeans, corn, wheat, and rice.

However, these derivatives have not been found to have any selectivity for the above crops.

Conventionally, many herbicides such as amide compounds, thiol carbamate compounds, and diphenyl ether compounds have been developed and put into practical use as herbicides for paddy fields, but their performance is still not sufficient. The amide compound butachlor is used before and after rice planting, but chemical damage to rice caused by temperature conditions has always been a problem. The use of the thiol carbamate compound molinate is regulated due to fish toxicity. In addition, penthiocarb poses a problem of phytotoxicity to paddy rice under reducing soil conditions. Diphenyl ether compounds, like butachlor, are used immediately after rice planting, but their activity drops significantly if the treatment is delayed.

All of these herbicides have excellent performance in some respects, so they are widely used and widely used, but their shortcomings and problems have gradually become apparent.
There is a strong need for new herbicides for rice fields that are easier to use and have superior performance.

On the other hand, as a fungicide, ethoxyacetothioamide derivatives described in JP-A-57-176958 are said to be effective against pudyl rot and tomato late blight. Captafor, TPN, cabtan, or dithiocarbamate drugs have been widely used to treat late blight and downy mildew of various crops, and have contributed to increased crop production. However, all of these compounds mainly have a preventive effect against late blight and mildew, and cannot be expected to have any therapeutic effect at all. Therefore, it has a major drawback in that sufficient effects cannot be expected even when the occurrence of disease is recognized. In reality, when considering the spraying of chemicals to control crops, it is more or less necessary to spray them after the disease has appeared, and it is difficult to completely control the disease with these compounds.

' In order to improve these points, research into new pest control agents has continued, and currently N-
Phenylalanine ester derivatives, such as metalaxyl (N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)alanine methyl ester), have been developed and are being put into practical use worldwide.However, these N-phenylalanine esters Derivatives have already become a problem due to their resistant bacteria.

In addition, the conventional method for producing amide-substituted acetothioamide derivatives (7) and the method proposed in JP-A-57-17693
No. 8 and No. 5B-69866), in the production of an acetonitrile derivative as a precursor, hydrolysis of the nitrile group occurs in the norogenization step to become a carbamoyl derivative.
A long process of obtaining an intermediate acetonitrile derivative by dehydrating the carbamoyl group was required, and the yield was low.

[Problem to be solved by the invention]

The present invention overcomes the drawbacks of the prior art described above, and provides a compound having extremely excellent properties as a herbicide for paddy fields and a fungicide for agriculture and horticulture, a method for producing the compound, and a noxious weed control agent containing the compound as an active ingredient. The objective is to provide a microbial control agent.

In other words, as a herbicide, it is suitable for use in paddy fields during a wide range of seasons, has little phytotoxicity to paddy rice, and has low toxicity to fish, and as a fungicide, it has preventive and therapeutic effects against late blight and downy mildew of various plants. Compounds with a wide range of applications that have both of the above and also have an excellent control effect on soil diseases such as seedling damping-off of various plants, simpler and higher-yielding methods for producing them, and containing them. An object of the present invention is to provide a useful agrochemical composition.

[Means and effects for solving the problem] As a result of intensive research on amide-substituted acetonitrile derivatives to solve the above-mentioned problem, it was found that substituted propargyloxyacetothioamide derivatives exhibit physiological activities that could not be predicted from the patent exemplified compounds. As a herbicide for paddy fields, it is suitable for a wide range of seasons, has little phytotoxicity to paddy rice, and has low toxicity to fish, while as a fungicide it is effective as a preventive and therapeutic agent against late blight, downy mildew, etc. of various plants. The present invention has been completed by discovering that the present invention has both the above-mentioned effects and also exhibits excellent control effects against soil diseases such as seedling damping-off of various plants.

The substituted propargyloxyacetothioamide derivative according to the present invention has the general formula (I) (wherein A represents a phenyl group, substituted phenyl group or naphthyl group, Ro represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, This is a new compound represented by the following formula (indicating a haloalkyl group spanning a lower alkyl group).

When A is a substituted phenyl group, examples of the substituent include a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group and a cyano group.

The present invention also provides a method for producing the substituted propargyloxyacetothioamide derivative represented by the general formula (1), which can be produced in substantially shorter steps and with higher yields, as a result of intensive studies to overcome the drawbacks of the prior art. The present invention was completed by discovering a method for obtaining the desired product at a low rate.

That is, the acid chloride represented by the general formula (II) A-coat (II) (wherein A has the above meaning) is reacted with aminoacetonitrile to form the general formula (1) % formula % (1) ( Acylaminoacetonitrile represented by the formula (wherein A represents the above meaning) is obtained, and this is treated with a halogenating agent to obtain the general formula NA-CONHCH (■ (where A represents the above meaning). , or a halogen atom), which is then reacted with t-substituted propargyl alcohol M (in the formula, R1 and R2 have the above-mentioned meanings) to form the general formula (to) (in the formula , A, R'' and R2 have the above meanings.)
Obtain an acylaminoacetonitrile derivative represented by
The general formula (
A method for producing a substituted propargyloxyacetothioamide derivative represented by 1) is provided.

The production method of the present invention is shown in a reaction scheme and explained below.

Reaction scheme (wherein A, R'' and R2 have the above meanings,)
:/'l: Indicates a 7-gen atom. ) General formula (11) A-
Acylaminoacetonitrile (1) is obtained by reacting an acid chloride represented by coat (in the formula, A represents a phenyl group, a substituted phenyl group, or a naphthyl group) with aminoacetonitrile. When this is treated with a halogenating agent in an appropriate solvent, a halogenated intermediate (Iv) is obtained. Examples of these solvents include aliphatic halides such as dichloromethane, chloroform, carbon tetrachloride, and 1,4-dichloroethane, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, and ethyl propionate, and carbon disulfide. However, good results can be obtained by using aliphatic carboxylic acid esters, especially ester solvents such as ethyl acetate. Bromine, chlorine, phosphorus oxychloride, sulfuryl chloride, phosphorus tribromide, etc. can be used as the halogenating agent.

The reaction temperature is in the range of 0 to 120°C, preferably at bag temperature. Since the rogogenated intermediate GV) is unstable, it is used immediately after its preparation. This metal halide (1) is reacted with substituted propargyl alcohol (3). This reaction can be carried out in the presence of an acid acceptor.

Examples of acid acceptors include organic bases such as triethylamine, dimethylaniline, pyridine, and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium carbonate.

This reaction is preferably carried out in a solvent or diluent.

Pyridine can be used both as a solvent and as an acid acceptor.

Since the thermal stability of the intermediate is poor in this reaction, it is undesirable to react at too high a temperature, and since it is an exothermic reaction, it is desirable to carry out the reaction under cooling.

At low temperatures, reaction intermediates tend to precipitate, slowing down the reaction rate and making it impractical, so it is desirable to carry out the reaction at -30 to 50°C, preferably -20 to 20°C.The thus obtained acylaminoacetonitrile derivatives By treating with gaseous hydrogen sulfide in a suitable solvent, the desired substituted propargyloxyacetothioamide derivative (1)' can be obtained. This reaction is accelerated by using a 6th class amine as a catalyst. Examples of tertiary amines include triethylamine, dimethylaniline, diethylaniline, pyridine, etc., but are not limited thereto. The reaction temperature is -2
It is carried out at a temperature of 0 to 100°C, preferably 20 to 50°C. The substituted propargyloxyacetothioamide derivative thus obtained can be easily isolated and purified by conventional methods such as recrystallization and column chromatography.

Furthermore, the present invention provides a herbicide for paddy fields and a fungicide for agriculture and horticulture, which contain the substituted propargyloxyacetothioamide derivative represented by the general formula (I) according to the present invention as an active ingredient. be.

When using the compound of the present invention as a herbicide for paddy fields, the application amount varies depending on the growth stage of the weed, the type of weed, the dosage form of the preparation, the application method, various environmental conditions, etc., but is usually 0.1 per area. -1001 is suitable, preferably 0.5-25f. Its herbicidal activity is characteristically strong against grass weeds, but it also shows a strong suppressive effect on other weeds even when they are not killed.

These characteristics are considered to be extremely advantageous when considering application by mixtures or tank mixes in some cases. In particular, the same tendency is observed for weeds of the Cyperaceae family, such as Cyperaceae and firefly, and also for other weeds, although the strength varies depending on the type of weed.

Furthermore, the timing of application of the compound of the present invention is wide ranging from before the emergence of weeds to the growing season. Compared to the known amide compound butachlor and the thiol carbamate compound benchocarb, the compound of the present invention has a much wider usable period and has superior characteristics not found in the past. Can be an easy herbicide. Although the practical dosage of herbicidal activity against Japanese millet naturally depends on the treatment time, penthiocarb and butachlor are insufficiently effective at practical dosages against Japanese millet at the 3.5-leaf stage, whereas the compounds of the present invention They exhibit sufficient activity for practical use at doses lower than their practical doses.

The compound of the present invention has extremely low phytotoxicity to transplanted paddy rice no matter when it is used at any time of treatment.

When the compound of the present invention is used as an agricultural and horticultural fungicide, it is not only effective against late blight and downy mildew of various crops caused by algal fungi, but also effective against diseases caused by various other plant pathogenic fungi. It is also effective.

The main diseases to be controlled are potato late blight, tomato late blight, tobacco late blight, strawberry late blight, adzuki bean stem blight, pudobe blight, cucumber blight, hotsupbe blight, shungikube blight, and various diseases caused by Aphanomyces spp., Pythium spp. One example is crop seedling damping-off.

Methods for applying the compound of the present invention include seed disinfection, foliage spraying,
Examples include soil treatment, but any application method commonly used by those skilled in the art will exhibit sufficient efficacy. The application amount and concentration will depend on the target crop, target disease, degree of disease occurrence,
Although it varies depending on the dosage form of the compound, application method, various environmental conditions, etc., when spraying, the amount of
is suitable, preferably 10 to 1001 per are.

A suitable spray concentration is 20 to 1.000 ppm, preferably 50 to 500 ppm.

The herbicide and agricultural and horticultural fungicide of the present invention may contain other biologically active compounds, such as other fungicides, insecticides, herbicides,
Not only can it be used in combination with agricultural chemicals such as plant growth regulators, soil conditioners, or fertilizing substances, but also mixed formulations with these are also possible.

Although the compounds of the invention may be applied neat, they are preferably applied in the form of a composition mixed with a carrier including a solid or liquid diluent. Carrier as used herein means an inorganic or organic substance, synthetic or natural, that is incorporated to aid in the delivery of the active ingredient to the area to be treated and to facilitate storage, transport and handling of the encased active ingredient compound. .

Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic substances such as diatomaceous earth, china clay, melk, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, vegetable organic substances such as soybean flour, sawdust, and wheat flour; Examples include urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene; paraffinic hydrocarbons such as kerosene and mineral oil; halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane; ketones such as acetone and methyl ethyl ketone; Examples include ethers such as dioxane and tetrahydro-7rane, alcohols such as methanol, propatool, and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used alone or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as genin sulfonate, nonionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, calcium stearate, wax, etc. lubricants, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to the above.

The amount of active ingredient in the composition of the compound of the present invention is usually 0 when used as a powder.
．． The amount is 5 to 20% by weight, 10 to 9% by weight for water preparations, 0.1 to 20% by weight for granules, 5 to 30% by weight for emulsions, and 10 to 90% by weight for flowable preparations.

〔Example〕

Representative examples of substituted propargyloxyacetothioamide derivatives represented by general formula (I) according to the present invention are shown in Table 1.

Next, the method for producing the compound of the present invention will be specifically explained by giving a synthesis example.

Synthesis Example-1 Synthesis of α-benzoylamino-propargyloxyacetothioamide (Compound No.-1) 1-1 Synthesis of α-benzoylamino-propargyloxyacetonitrile Benzoylaminoacetonitrile 4 synthesized from benzoyl chloride and aminoacetonitrile by a conventional method 4.0? of bromine in 200 ml of ethyl acetate solution at room temperature. added at once. When the color of bromine in the reaction solution disappears, the reaction solution is cooled to below 0°C, and propargyl alcohol 1.549
- and 5.62 ml of triethylamine were dissolved in 10 rnl of tetrahydrone run, and added dropwise to the previously cooled ethyl acetate solution. After the dropwise addition was completed, the reaction was continued at room temperature for an additional 30 minutes. After the reaction was completed, triethylamine bromate was divided into portions from the reaction mixture, and the r liquid was distilled under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography. Elute with a hexane-ethyl acetate system, distill the solvent off from the eluate, and prepare α-benzoylamino-propargyloxyacetonitrile as a solid with a concentration of 3.7? Obtained. Yield 69
．． 2%, m, p, 61-71°C.

The acylaminoacetonitrile used as a starting material can be easily produced by reacting an acyl halide with aminoacetonitrile in a conventional manner.

For example, a 10% aqueous sodium hydroxide solution is cooled in ice water, and aminoacetonitrile sulfate is added and dissolved while stirring. To this solution, a toluene solution of acid/ride is added dropwise while cooling with water, and after the dropwise addition is completed, the mixture is further stirred at the same temperature. The precipitated crystals were filtered under suction, and the resulting crystals were washed with toluene and then with water, and then dried, and used.

1-2 Synthesis of α-penzoylamino-prono(lugyloxyacetothioamide) α-benzoylamino-propargyloxyacetonitrile 2.Off, 1.0 l of triethylamine was dissolved in 50 mA of toluene. Hydrogen sulfide was added to this solution at room temperature. After the reaction was completed, it was cooled in a water bath, and the precipitated crystals were filtered with suction to obtain α-benzoylamino-propargyloxyacetothioamide as a white solid.
Obtained. Yield 90.6%, m, p, 97-102°C.

NMRa ac""-" (ppm): 2.92 (I
ILt), 4.43 (2H,d), MS 6.12 (IH,d), 7.3-8.1 (5H.

m), 8.3 (IH, d), 9.1 (2H.

bs) Synthesis Example-2 α-(3,5-dichlorobenzoylamine)-propargyloxyacetothioamide (Compound No.-9) α-(3,5-dichlorobenzoylamine)-propargyl obtained in the same manner as in 1-1. Oxyacetonitrile 2.
01 with pyridine 30m/! dissolved in Hydrogen sulfide is passed into this solution at room temperature for 2 hours. After the reaction was completed, pyridine was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. The desired α-(3,5-dichlorobenzoylamino)-propargyloxyacetothioamide was eluted from a hexane-ethyl acetate system as a white solid at 1°8? Obtained. Yield 80.3%, m, p, 1
65-170°C (decomposition).

Next, the method for formulating the herbicide for paddy fields or the fungicide for agricultural and horticultural use of the present invention will be explained using formulation examples.

The active ingredient compounds are shown by compound numbers in Table 1 above. "Parts" represent "parts by weight."

Formulation Example-1 Powder Compound (1): 3 parts, diatomaceous earth: 20 parts, white clay:
30 parts and 47 parts of talc were uniformly ground and mixed to obtain 100 parts of a powder.

Formulation Example-2 Wettable powder Compound (2): 30 parts, diatomaceous earth: 44 parts, clay: 20 parts, sodium ligninsulfonate: 1 part and sodium alkylbenzenesulfonate: 2 parts were uniformly ground and mixed and hydrated. 100 parts of the agent were obtained.

Formulation Example 3 Emulsion Compound (3): 20 parts, 10 parts of cyclohexanone, 50 parts of xylene, and 20 parts of Tulpol (surfactant manufactured by Toho Chemical Co., Ltd.) were uniformly dissolved and mixed to obtain 100 parts of an emulsion.

Formulation Example-4 Granule Compound (4): 1 part, bentonite 278 parts, Merck: 20 parts and sodium ligninsulfonate: 1 part were mixed, an appropriate amount of water was added and kneaded, and then extrusion granulation machine was used. After granulation and drying by a normal method, 100 granules
I got the department.

Formulation Example-5 Granules Compound (10): 7 parts, polyethylene glycol nonylphenyl-c-thyl: 1 part, polyvinyl alcohol = 3 parts, and 789 parts of clay were uniformly mixed, and after hydrogranulation, it was dried to give a granule of 100 parts. I got the department.

Formulation Example-6 Powder Compound (6): 2 parts, calcium carbonate: 40 parts, and 258 parts of clay were uniformly ground and mixed to obtain 100 parts of a powder.

Formulation Example 7 Wettable powder Compound (5): 50 parts, Merck: 40 parts, sodium lauryl phosphate: 5 parts, and sodium alkylnaphthalene sulfonate: 5 parts were mixed to obtain 100 parts of a wettable powder.

Formulation Example-8 Wettable powder compound (6): 50 parts, sodium ligninsulfonate: 10 parts, sodium alkylnaphthalene sulfonate = 5 parts, white carbon: 10 parts, diatomaceous earth: 2
5 parts were mixed and ground to obtain 100 parts of a wettable powder.

Formulation Example-9 Flowable agent compound (40 parts of crab, carboxymethyl cellulose: 3
1 part, sodium ligninsulfonate = 2 parts, dioctyl sulfosuccinate sodium salt = 1 part, and 54 parts of water were wet-ground in a sand grinder to obtain a flowable agent 1.
I got 00 copies.

Next, the herbicide efficacy of the compound of the present invention will be explained using test examples.

Test Example 1 Paddy field pre-emergence weed control test R/Fill soil in a 5000 Wagner pot, and test for weeds such as Japanese millet, broad-leaved weeds (Kikashigusa, Azena, Prunus japonicus, etc.).
Seeds of firefly, Heraomodaka, and Tamagayatsuri were sown, and the area was flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. One day after transplanting paddy rice and before weeds appeared, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 5 above. Processing 30
A day later, weed growth and chemical damage to paddy rice were investigated. The results are shown in Table-2.

In the table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the emergence or growth of crops or weeds with that of the untreated air-dried type according to the evaluation criteria below. The test compounds were indicated by compound numbers in Table 1 above (the same applies hereinafter).

Evaluation standard 0: Survival rate shown by air dry weight ratio vs. untreated area 91-100
%1: 71-90
%2: 41-70
%3: 11~4
0% 4: 6-1
0%5: 0~5
% Test Example 2 Rice paddy growing season weeding test R/5.000 Fill a Wagner pot with soil, and fill it with Japanese millet, broad-leaved weeds (Kikashigusa, Azena, Prunus japonicus, etc.)
Seeds of , firefly, yellowtail, and cyperus were sown and flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. During the weed growth period 12 days after transplanting paddy rice, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 4 above. Thirty days after the treatment, weed growth conditions and chemical damage to paddy rice were investigated, and the results are shown in Table 3. In this table, the degree of chemical damage to crops and the growth status of weeds were expressed according to the method shown in Test Example 1.

The results shown in Tables 2 and 3 show that the compounds of the present invention can be used in pre-emergence treatments against various noxious weeds that are a problem in rice fields, and also in Z-growth season treatments, where it has been difficult to achieve herbicidal effects. It is clear that it is an excellent compound that exhibits a wide range of herbicidal activities and has almost no phytotoxicity to paddy rice.

Furthermore, a group of compounds disclosed in JP-A-57-176938, namely α-(3-chlorobenzoylamine)-ethoxyacetothioamide or α-(3,4-
Dichlorobenzoylamino)-ethoxyacetothioamide, etc., showed phytotoxicity to paddy rice in a rice field pre-emergence herbicide test and was not selective as a herbicide for paddy fields, whereas the compounds of the present invention did not show any phytotoxicity to paddy rice. It is clear that the compound exhibits excellent selectivity and has excellent properties that could not be expected from the compound disclosed in JP-A-57-176938.

Next, the efficacy of the agricultural and horticultural fungicide of the present invention as a fungicide will be explained using test examples.

Test Example-3 Potato Phytophthora Control Test Potatoes grown in pots in a greenhouse (variety: Otokoshaku, plant height approximately 25 cIIL) were treated with a prescribed concentration of the drug (test compound was applied as a hydrating agent according to the method of Formulation Example-2). , diluted with water to a predetermined concentration) with a spray gun (1,0k
g/cd) and sprayed 501 nl per 3 pots and air-dried. A zoospore suspension was prepared from potato Phytophthora blight which had been previously cultured on potato sections for 7 days. This suspension was spray inoculated onto the potato plants sprayed with the drug, and the test plants were kept at 17-19° C. and a humidity of 95% or higher for 6 days, and then the degree of lesion formation was investigated.

Observe and evaluate the lesion area ratio for each leaf to determine the disease severity index.
The degree of morbidity was determined for each ward using the following formula.

The evaluation criteria are as follows.

Disease severity index O: Lesion area ratio 0%1:
〃 1-5% 2: 〃 6-25% Disease severity index 3: Lesion area ratio 26-50% 4:
// 51% or more n1: Disease severity index 0
0 leaf number (12: // l // n3: " 2 〃 n4: // 3 // ns: //
4 // The results are shown in Table-4.

Control compound A: α-(3-chlorobenzoylamine)-ethoxyacetothioamide B: α-(3,4-dichlorobenzoylamine)-ethoxyacetothioamide E: Zinc ethylene bis(dithiocarbamate) F: Tetrachloroisophthalonitrile Control compounds A and B are compounds disclosed in JP-A-57-176938.

E and F are commercially available agents for controlling potato late blight and cucumber blight.

(Common to the following test examples) Test example-4 Kyuuribe and disease control test (preventive effect) Cucumbers grown in pots in a greenhouse (variety: Sumo Hanshiro, True Leaf 2)
Spray a drug (1,000 kg/crI) at a predetermined concentration (preparing a wettable powder of the test compound according to the method of Formulation Example 2 and diluting it with water to a predetermined concentration) onto a 3 Qml was applied per 3 pots and air-dried. Downy mildew bacteria were collected from lesions on cucumber leaves infected with downy mildew, a spore suspension was prepared with demineralized water, and the suspension was sprayed for inoculation. The inoculated pots were immediately kept at 18-20° C. and a humidity of 95% or higher for 24 hours, then transferred to a greenhouse (room temperature 18-27° C.), and after 7 days, the degree of lesion formation was examined.

The evaluation criteria and disease severity display method are as shown in Test Example-3.

The results are shown in Table-5.

Table-4 Potato Phytophthora control test Table-5 Chieuripe blight test From the results shown in Table-4 and Table-5, the compounds of the present invention are clearly effective against potato late blight and plant diseases caused by cucumber and fungi. It is clear that it has a high pesticidal effect. In addition, the compounds of the present invention are disclosed in JP-A-57
-176938, namely α-
It is clear that (3-chlorobenzoylamine)-ethoxyacetothioamide, α-(3,4-dichlorobenzoylamino)-ethoxyacetothioamide, etc. have an unexpected excellent control effect.

〔Effect of the invention〕

As is clear from the above explanation, the substituted propargyloxyacetothioamide derivative according to the present invention exhibits a wide range of excellent herbicidal effects as a herbicide for rice fields during the appropriate season, which could not be expected with conventional herbicides, and also As a horticultural fungicide, it shows preventive effects against various diseases caused by algae and fungi on various crops, including soil diseases, at low dosages and concentrations where conventional commercially available drugs cannot be expected to be effective, and also has therapeutic effects. Has excellent pest control properties. The agricultural chemical containing the substituted propargyloxyacetothioamide derivative according to the present invention has excellent properties and is useful as a herbicide and a fungicide for agriculture and horticulture.

Claims (4)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A represents a phenyl group, substituted phenyl group, or naphthyl group, and R^1 represents a hydrogen atom or a lower alkyl group. and R^2 represents a hydrogen atom, an alkyl group or a haloalkyl group). (2) A patent in which, in general formula (I), A is a phenyl group substituted with one or more of a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group, or a cyano group. Claim 1
Substituted propargyloxyacetothioamide derivatives as described in . (3) General formula (II) A-COCl(II) (wherein A represents a phenyl group, substituted phenyl group, or naphthyl group) is reacted with aminoacetonitrile to produce general formula (III) Acylaminoacetonitrile represented by A-CONHCH_2CN(III) (in the formula, A indicates the above meaning) is obtained, and this is treated with a halogenating agent to form the general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(IV) Obtain a halogenated intermediate represented by (in the formula, A indicates the above meaning and X indicates a halogen atom), and then substitute this with propargyl alcohol (V) ▲ Numerical formula, chemical formula, table, etc. ▼ (V) (In the formula, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom, an alkyl group, or a haloalkyl group) to form the general formula (VI) ▲ Formula, There are chemical formulas, tables, etc. ▼ (VI) (In the formula, A, R^1 and R^2 indicate the above meanings)
Obtain an acylaminoacetonitrile derivative represented by
The general formula (
I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A represents a phenyl group, a substituted phenyl group, or a naphthyl group, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a A method for producing a substituted propargyloxyacetothioamide derivative represented by a hydrogen atom, an alkyl group, or a haloalkyl group. (4) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A represents a phenyl group, substituted phenyl group, or naphthyl group, and R^1 represents a hydrogen atom or a lower alkyl group. A herbicide for rice fields or a fungicide for agricultural and horticultural purposes, which contains as an active ingredient a substituted propargyloxyacetothioamide derivative represented by the following formula (wherein R^2 represents a hydrogen atom, an alkyl group, or a haloalkyl group).